Manifestation of predissociation and vibrational relaxation in femtosecond pump–probe signals: a theoretical analysis

Classical molecular dynamics (MD) is used to study vibrational relaxation and predissociation processes in I2 embedded in a rare-gas environment. It is shown that the simultaneous effect of the two mechanisms determines the deviation of experimental pump–probe signals from a single-exponential decay [Lienau and Zewail, J. Phys. Chem. 100 (1996) 18629].